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Issue 4, 2001
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Structure, optical and magnetic behaviour of meso-tetraphenylporphyrinatoiron(III) tetracyanoethenide, [FeIII(TPP)]+[TCNE]˙

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Abstract

The direct redox reaction between tetracyanoethylene (TCNE) and meso-tetraphenylporphyrinatoiron(II), [FeII(TPP)], formed the electron transfer salt (ETS) [FeIII(TPP)][TCNE], which has been structurally, spectroscopically, and magnetically characterized. It has an extended one-dimensional linear chain with coordination polymer motif comprised of [FeIII(TPP)]+ and bridging μ-[TCNE]˙ with Fe–NTCNE distance 1.889(2) Å. This coordination geometry is consistent with a low-spin iron(III) ion, i.e., one electron transfer from FeII to TCNE produces S = 1/2 [FeIII(TPP)]+ having a (dxy)2(dyz,dzx)3 configuration and S = 1/2 [TCNE]˙. 57Fe Mössbauer data, δ = 0.28 mm s−1 and ΔE = 2.19 mm s−1 at 77 K, also support the low-spin state. The room temperature magnetic moment of the ETS, 1.20 μB, arises from two S = 1/2 systems having antiferromagnetic coupling, −190 cm−1 (H = −2Σ Ji jSiSj).

Graphical abstract: Structure, optical and magnetic behaviour of meso-tetraphenylporphyrinatoiron(III) tetracyanoethenide, [FeIII(TPP)]+[TCNE]˙− [ ]

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Article information


Submitted
02 Oct 2000
Accepted
04 Dec 2000
First published
18 Jan 2001

J. Chem. Soc., Dalton Trans., 2001, 448-455
Article type
Paper

Structure, optical and magnetic behaviour of meso-tetraphenylporphyrinatoiron(III) tetracyanoethenide, [FeIII(TPP)]+[TCNE]˙

S. Mikami, K. Sugiura, T. Maruta, Y. Maeda, M. Ohba, N. Usuki, H. Ōkawa, T. Akutagawa, S. Nisihara, T. Nakamura, K. Iwasaki, N. Miyazaki, S. Hino, E. Asato, J. S. Miller and Y. Sakata, J. Chem. Soc., Dalton Trans., 2001, 448
DOI: 10.1039/B007931F

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